Since the early 90s, Italy has undergone radical changes in the regulations of the public pension system aimed at mending its main drawbacks and improving sustainability in the long run. The reforms were intended to recover the national economy through a significant reduction of benefits by increasing, particularly for younger people, individual responsibility for the accumulation of retirement wealth. Adopting an enhanced version of the Theory of Planned Behavior (TPB), which includes affective reactions, the present paper aims to understand the factors influencing the intention to enroll in a private pension plan through the purchase of longevity annuity coverage on the part of young adults. A purposive sample of 7480 Italian people aged 25–35 participated in the survey. Collected data were analyzed adopting an ordinal logistic regression (OLR) model. The findings confirm the predictive power of the TPB in the financial field of longevity annuity buying, show that anticipated affective reactions increase the predictive power of the TPB model, and reveal that the influence of the investigated constructs varies alongside people’s willingness to purchase. The outcomes provide useful recommendations to the policy maker and private companies to favor the adoption of wide-spread desired behaviors among citizenships.